The present invention relates to an industrial material with fluorine passivated film and process of manufacturing the same, and more particularly to an industrial material such as metal, ceramics or plastics whose surface has a film passivated by fluoridation and which is preferably applicable to a manufacturing field of semiconductors, and to a process of manufacturing the above industrial material.
In general, in the process of manufacturing semiconductors, specific gases of high reactivity and corrosiveness such as BCl.sub.3, SiF.sub.4, WF.sub.4, or the like are used, and therefore hydrolysis occurs under the atmosphere of moisture, resulting in generation of highly corrosive acid such as hydrogen chloride, hydrogen fluoride or the like. Accordingly, when using some metal material such as aluminum or aluminum alloy as storage containers, pipelines, reaction chambers and the like for treating the above gases, there unavoidably arises a serious problem that such metal material is caused to corrode easily.
Recently, semiconductor devices have been small-sized to improve integration thereof, and various researches and developments have been made so that semiconductor devices are small-sized in the range of 1 .mu.m to submicron of smaller than 0.2 .mu.m may be put into practical use.
In order to improve the integration of semiconductor devices, it is necessary for semiconductors to be manufactured by the process which is kept at low temperature and with high selectivity in terms of material of substrate, thus a highly purified process atmosphere is required. In the case where an apparatus necessary for such a highly purified process atmosphere corrodes slightly, impurities produced as a result of such corrosion may be mixed with wafer of semiconductor devices, resulting in deterioration of quality of film and making it impossible to achieve accuracy of fine processing. Consequently, reliability essential for ultra-fine semiconductor devices, i.g., ULSI is lowered.
Further, in the field of excimer laser using a laser containing rare gases such as argon, krypton or xenon, or halogen gases together with rare gases, a laser oscillator is caused to corrode by fluorine due to corrosion of inside of the apparatus, thus shortening the life of the apparatus.
Furthermore, in the apparatus for treating particular halogen gas such as RIE performing directional chemical etching which is used for manufacturing integrated circuits, or CVD performing chemical vacuum evaporation to precipitate a film of reaction product by feeding a volatile compound of material to be precipitated onto the substrate and then pyrolysis or reaction thereof, the employed gas is reacted with moisture absorbed on metal surface or oxidation film of metal surface, thus generating secondary corrosive gas and resulting in secondary pollution of atmosphere in the apparatus.
In order to solve the above drawbacks, conventionally, a grounding film is formed on the metal surface by means of electroplating, vacuum evaporation or sputtering or the like, fluorine passivated film is formed on the grounding film of the metal surface, thereby preventing the metal surface from being corroded by the above-mentioned secondary corrosive gas. Such technology is disclosed in, for example, the Laid-Open patent publications No. 2-175855, No. 2-263972.
However, since the semiconductor manufacturing apparatuses, the excimer laser, and pipes attached to the apparatuses have mostly complicated shape, the grounding film cannot be uniformly formed on the inside surface of the apparatuses by means of electroplating, vacuum evaporation or sputtering or the like. Consequently, the fluorine passivated film cannot be formed on the grounding film, sufficient corrosion resistance to corrosive gas of the halogen series cannot be obtained.
Further, in the field of manufacturing semiconductors, in the case of where phosphorus is exposed on the metal surface, there occurs doping upon sputtering. Therefore, it is necessary not to expose phosphorus on the metal surface.
On the other hand, in the process of manufacturing semiconductors, nonmetal material such as plastics, ceramics or the like besides the above-mentioned metal material is used. When using the nonmetal material in the process of manufacturing semiconductors, it is necessary to form fluorine passivated film on the surface of the material to prevent gas from being released from the surface of the material or to obtain conductivity. Incidentally, in case of plastics, the fluorine passivated film must be also formed on the surface of the material from the viewpoint of corrosion resistance.